Diqtjinonyl amides in vat color



Patented Mar. 6, 1945 DIQUINONYL ALHDES IN VAT COLOR COMPOSITIONS Roy Herman Kienle and Chester Albert Amick,

Bound Brook, N. .L, assignors to American CyanamidCompany, New York, N. Y., a corporation of Maine No Drawing. Application July 1, 1943,

Serial No. 493,134

Claims.

subject to these difiiculties, do not require these agents but they usually contain agents or are so processed as to promote dispersibility.

In either case, the dye paste or dye powder must be admixed with suitable thickener, usually a gum dispension, to form a printing-color paste which is suitable for application. In the case of vat dyes, it is also necessary to add a reducing agent and usually an alkali. Because the color yield from printing-color pastes often decreases rapidly as the paste ages after being made up, these printing-color pastes are usually prepared by the fabric finishers just before they are to be used.

The printing-color pastes, however compounded, are then applied to textile, paper or other fabric materials fordecorative or protective purposes. The printed pieces are dried, aged in a steam ager, treated with an oxidizing agent, rinsed and finally dried. Usually in processing textiles, the printed fabric also is soaped at or near the boil with about a 0.1% soap solution and again rinsed before the final drying operation.

In making up and applying printing-color pastes it has been found that a material suitable for use as a printing assistant is of advantage in obtaining maximum color yield. The exact way in which these materials act to produce an improved color yield in printing is not entirely understood. It is with these printing aids or assistants that the present invention is particularly concerned.

Although printing aids are desirable in the printing-color pastes, the exact point at which they are added may vary. Dye pastes'may contain printing aids as one of their components and printing-color pastes made therefrom will obviously contain the printing assistant. Where a printing assistant is not present in the dye paste, it may be added at the time of making up the. printing-color paste.

, It is preferable, however. that the Drinting assistant be incorporated in the actual dye paste.

Their addition at the proper point in the manuii fore, the objector the present invention to profacture of the paste is not only easier, but in addition they are thus generally more uniformly dispersed throughout a printing-color paste made therefrom. As a result, the printing assistants usually operate more eflectively when the printing-color paste is finally applied to the fabric.

It is only relatively recently that dye powders suitable for use in making up printing-color pastes have been available. Most, of the printing aids previously used in dye pastes, being either liquid in form or extremely hydroscopicycan not be used with dye powders, the latter being necessarily limited to the use of dry solids. Nevertheless, it is desirable that printing assistants be incorporated 'in the powders at the time of manuiacture for the same reasons which apply in the case of dye pastes.

Dye pastes containing various liquid printing assistants have been made. Among the liquid materials-used are the alkylol amines, for example, triethanol amine; and/or polyhydric alcohols such as glycerine, glycol, diethylene glycol and the like. Various derivatives therefrom also have been tried. If a printing aid is to be incorporated in a dye powder, a solid printing aid is necessary. Examples of such solids which have been used in the past include the hydrochlorides of alkylol amines; silver salt (sodium anthraquinone betasulfonate) anthraquinone and certain metal salts such as-those of cobalt and iron.

Unfortunately, most of these printing aids previously used are not as satisfactory as may be desired. Many of them will not in all cases produce the intensification of color for which they were intended. Others, such as the polyhydric alcohols, cause deterioration of the printingcolor pastes so that marked variations in the strength of prints therefrom are observable even after the printing-color paste has been allowed to stand for only a relatively short time. Many of them are satisfactory with some colors but have an adverse efiect on others, even to the extent of visibly altering the shade. None of them are suitable without modification for use both in,paste and powder compositions.

- There remains, therefore, a demand for suitable printing assistants which will produce a satisfactory color intensification and will not cause deterioration of the dyeing or printing composition on standing. Preferably also, the assistants should be useful both with dye pastes and dye powders and in addition should be readily available or cheaply and easily prepared. It is, therevide a new type of printing assistant which possesses these desirable properties.

In general, the object of the present invention is accomplished by making use of one or more of the diquinonyl carboxylic acid diamides as 5 printing assistants. These compounds may be generically represented by the type formula in which Ac represents the residue of a cyclic or So far as the present invention is concerned, the assistants may be added to the.printing-color pastes at any point in the preparation of the latter.. They may be incorporated into the thickener; into the dye pastes or powders or may be blended directly into the printing-color paste. However, as pointed out above, it is preferable that they be incorporated in the dye paste or powder during manufacture.

The use of this new class of printing assistants possesses a number of important advantages. These compounds are dry solids, which may be readily powdered and blended in dye powders and aresoluble or dispersible in dye paste suspensions. They have, therefore a general application in both dye pastes and dye powders. They do not cause deterioration of printing-color pastes on standing. They encourage the production of excellent color yields even under hot ageing conditions. Their use is simple sincethey may be employed as powders or as suspensions in water or alcohol, producing excellent color yields whatever the mode of admixture.

In preparing the compounds to be used as the printing assistants of the present invention the dicarboxylic acid may be quite widely varied. The compounds may -be derived from either cyclic or aliphatic dicarboxylic acids. Of the cyclic dicarboxylic acids, phthalic acid is perhaps the most common and its derivatives have been found to give good results when used according to the present process. The invention however is not meant to be so limited but includes, for example, derivatives of isophthalic, terephthalic, polyhydrophthalic acids, the endoalkylenepolyhydrophthalic acids such as endomethylene tetrahydrophthalic and endoethylene hexahydrophthalic acids and the like, and the naphthalic acids, as well as substituted acids derived therefrom.

Where derivatives of aliphatic carboxylic acids are used, the original acid or anhydride may be- 1 varied over a considerable range. If the original acid is considered to have the formula COOH COOH

/C O H20 I 0 in the case of the anhydride, C in the generic formula may vary over the range of 11:0 in the case of oxalic acid to about 1 :13 without departing from the scope of the present invention. However, where y is greater than about 6, trouble is encountered in preparing the derivatives. Above about y:8, there is a tendency for the compounds to become sufficiently water insoluble to prevent satisfactory use. The acids may be either saturated acids such as malonic, succinic, glutaric, adipic, azelic, sebacic and the like or unsaturated such as maleic, fumaric and the like.

As pointed out in connection with the generic formula, Q and Q represent quinonyl groups such as those of the naphthoquinones and anthraquinones. Paraquinonyl derivatives such as those from alpha-naphthoquinone and panthraquinone were found to give particularly good results according to the present invention.

The invention however is not necessarily so limited. Similarly good results were obtained for example from the derivatives of beta-naphthoquinone and 'beta-anthraquinone. While the theoretical possibilities do not require that Q and Q be the same quinonyl radicals, practically the present invention is so ilmited. Similar compounds in which Q and Q are not identical are considered in our copending applications for U. S. Letters Patent, Serial Nos. 493.1354, filed of even date.

While the dye and printing-color paste compositions of the present invention are not limited to the use of any particular dyes or dye forms, they are especially suitable for use with vat-dyes in either paste or powder form. Particularly good results may be obtained using the vat-dye powders of high autodispersibility set forth in Crossley et al., United States Reissue Patent No. 21,402, reissued March 19, 1940. By combining the color materials of that patent into printing paste compositions containing the assistants of the present invention, the full advantages of both may be gained with a resultant simplicity in use, excellence of shade and sharpness of color.

Printing pastes made in this way have the particular advantage that the dyes remain in a highly dispersed state as individual particles rather than as dispersions of particle aggregates. In the present specification and claims, where highly-dispersed dyes are referred to, reference to pastes in which the dye particles are so dispersed is intended;

The invention will be more fully set forth in connection with the following examples which are intended to be illustrative and not by way of limitation. All parts are by weight unless otherwise noted.

In the succeeding examples, test prints were made on two different fabrics. Where rayon is referred to, a titanium-dioxide-pigmented, allviscose-rayon flat crepe was used. The cotton fabric referred to is an 80 x 80 bleached, un-

ings referred to as plant or hot ageings were carried out in the temperature range of about l06-l10 C. In the case of the cotton prints ageing periods of 3 minutes, 5 minutes or both were used. The shortest period which gives a satisfactory ageing is preferable.

Example 1 which time 700 parts of sodium sulfoxylate were.

dissolved therein, 600 parts of .glycerine were added and the paste bulked to about 10,000 parts. Stirring was continued until the paste cooled to room temperature. In the succeeding examples this paste is referred to as thickener A.

Example 2 720 parts of 13-2 British gum and 720 parts of KAC-4 gum (Stein Hall) were added to 5,600 parts of water and heated over a steam bath for approximately 1 hours after the temperature reached 185-190 F. The source of heat was then removed but stirring was continued until the temperature decreased to 120 F. at which time 1,200 parts ofpotassium carbonate which had been previously dissolved in 1,000 parts of water was added to the cooked gum. 1,560 parts of sodium sulfoxylate formaldehyde were dissolved in 1,500 parts of water at a temperature of about 140 F. and added to the common mixture with stirring until the whole was thoroughly mixed. Finally, 360 parts of glycerine were added and after thorough stirring the whole was bulked to 12,000 parts. In the succeeding examples this mixture is referred to as thickener B.

/ Example .3

6 parts of a dispersible Orange R powder (C. I.121l) prepared according to U; S, Reissue Patent 21,402 and containing about 2.4 parts of realdye, were pasted with 3 parts of water and 91 parts of thickener A. This was used as the control sample. 20 parts of N,N' di(beta-anthraquinonyl) fumaric acid amide were slurried with 80 parts of water and ground in a ball mill until a uniform suspension was obtained. 3 parts of Example 4 The procedure of Example 3 was repeated except that-3 parts of a 20% suspension of 11.1!

' di(alpha-anthraquinonyl) Iumaric' acid amide were used instead of the beta product of Example 3. The prints made from the'paste containing the printing assistant were smoother, brighter and appreciably stronger than those made from the paste containing water only.

Example 5 The procedure of Example 3 was duplicated exactly except that a 3% suspension of N,N' di(alpha-anthraquinonyl) maleic acid amide was used. Again the prints obtained from the paste containing the amide of 'maleic acid were much stronger both on rayon and cotton pieces than those obtained from the control sample.

Example 6 The procedure of Example 3 was duplicated except that a 3% suspension of N,N' di(betaanthraquinonyl) maleic acid amide was used.

Prints obtained from the paste containing the amide of maleic acid were much stronger, smoother and brighter.

Example 7 The procedur of Example 3 was followed except that the di-anthraquinonyl amide of fumaric acid was replaced-by the di-anthraquinonyl amide of phthalic acid. Both the di-alpha or the dibeta compound were used. Prints made from pastes containing both the di-alpha and the dibeta anthraquinonyl amides of phthalic acid were definitely superior to those obtained from the control sample.

Example 8 The procedure of Example 3 was repeated exactly except that the fumaric acid amide was replaced by N,N' di(anthraquinonyl) succinamide. In this case also. both the beta and the alpha compound were used. Prints obtained from the pastes containing the di-anthraquinonyl amides gave much stronger color yields than those made from the pastes containing water only. These assistants had the property of reducing the length of time that was necessary to develop the maximum color value during the ageing operation- This is a distinct advantage because it permits a speedup in the ageing operation, an important com mercial consideration.

- Example 9 6 parts of the alpha-anthraquinonyl diamide of fumaric acid were slurried in 94 parts of water and then milled in a ball mill for 18 hours. 5 parts of Golden Orange G powder (C. I.1096), prepared according to U. S. Reissue Patent 21,402 and containing about 1 part of real dye were slurried with ,5 parts of the 6% suspension of the alpha-anthraquinonyl diamide of furnaric acid. After the mixture was intimately mixed, 90 parts of thickener B were added. 5 parts of Golden Orange Gwere then slurried with 5 parts of water and 90 parts of thickener B to provide a control sample. Each of the pastes Were printed on rayon. The printed pieces were then air-dried, aged. oxidized, rinsed. scaped in 1 s soap solution for 5 minutes at the boil, then rinsed and ironed dry. The prints obtained from the paste containing' the alpha-anthraquinonyl diamide of fumaric acid were stronger and. brighter than those obtained from the control. This was particularly noticeable when. aged under practical mill conditions.

Example 10 A sample of wet presscake of Orange R, (C. I.- 121'7) was dispersed with" the sodium salt of disulfodinaphthyl methane and adjusted with water to contain about 12% real dye. 10 parts ofthis slurry were mixed with the printing assistant used in Example 9. Then to this mixture was added parts of thickener B and the whole was thoroughly mixed. A second 10 parts of the Orange R was likewise mixed with parts of water and 85 parts of thickener B. Prints made from the paste containing the printing assistant were much stronger both on cotton and rayon than those obtained from the paste containing water only.

Example 11 parts of Dark Blue BO dispersed powder, (C. I.-1099) prepared according to U. S. Reissue Patent 21,402 and containing about 3.7% real dye were dry blended with 0.3 parts of N,N' di(alphaanthraquinonyl) fumaramide. To this mixture. 90 parts of thickener B were added and after intimate mixing prints were made of this paste on cotton and rayon. A second 10 parts of the Dark Blue 130 were then mixed with thickener B without any printing assistant being added. This was the control sample. Thi paste was also printed on cotton and rayon. The prints obtained from the paste containing the printing assistant were definitely stronger and brighter than those obtained from the control sample. Again this was especially noticeable when plant ageing conditions were simulated.

Example 12 'I'heprocedure of Example 10 wa followed except that the diamide of fumaric acid was replaced by the reaction product of 2-amino-alphanaphthoquinone and maleic acid and of 5-aminoalpha-naphthoquinone and maleic acid. The prints obtained from the pastes containing the printing assistants were much stronger than those obtained from the paste containing water only.

We claim:

1. A color composition comprising a vat dye and a dicarboxylic acid diamide represented by the formula in which Ac represents the residue of a dicarboxylic acid selected from the group consisting of the saturated and unsaturated aliphatic dicarboxylic acids of from 2-10 carbon atoms, the phthalic acids, the naphthalic acids, the Dolyhydrophthalic and naphthalic acids and the alkyl-substituted phthalic and naphthalic acids, and Q and Q represent thesame quinonyl radicals selected from the group consisting of the naphthoquinonyl and anthraquinonyl radicals.

3. A dye composition comprising a vat dye powder of high autodispersibility, and a powdered dicarboxylic acid diamide represented by the gen eral formula in 'which Ac represents the residue of a dicarbox-.

ylic acid selected from the group consisting of the saturated and unsaturated aliphatic dicarboxylic acids of from 2-10 carbon atoms, the phthalic acids, the naphthalic acids, the polyhydrophthalic and naphthalic acids and the alkyl-substituted phthalic and naphthalic acids, and Q and Q represent the same quinonyl radicals selected from the group consisting of the naphthoquinonyl and anthraquinonyl radicals.

4. A color composition according to claim 1 in which Q and Q represent a naphthoquinonyl group. i

5. A color composition according to claim 1 in which Q and Q represent an anthraquinonyl group.

6. A printing paste composition comprising a vat dye, a thickener and a dicarboxylic acid diamide represented by the general formula in which Ac represents the residue of a dicarboxylic acid selected from the group consisting of the saturated and unsaturated aliphatic dicarboxylic acids of from 2-10 carbon atoms, the phthalic acids, the naphthalic acids, the polyhydrophthalic and naphthalic acids and the alkyl-substituted phthalic and naphthalic acids, and Q and Q represent the same quinonyl radicals selected from the group consisting of the naphthoquinonyl and anthraquinonyl radicals.

8. A printing paste composition comprising a highly-dispersed thio-indigo vat dye, a thickener and a dicarboxylic acid diamide represented by the general formula in which Ac represents the residue of a dicarboxylic acid selected from the group consisting of the saturated and unsaturated aliphatic dicarboxylic acids 01' from 2-10 carbon atoms, the phthalic acids, the naphthalic acids, the polyhydrophthalic and naphthalic acids and the alkyl-substituted phthalic and naphthalic acids, and Q and Q represent the same quinonyl radical selected from the group consisting of the naphthoquinonyl and anthraquinonyl radicals obtainable by compounding a collodized vat dye powder of high autodispersibflity and the dicarboxylic acid diamide with the thickener.

. 9. A method of printing with vat colors which comprises printing afabric with a printing paste composition comprising a vat dye. a thickener and a dicarboxylic acid diamide represented by the general formula acids of from' 2-10 carbon atoms, the phthalic acids, the naphthalic acids, the polyhydrophthalic and naphthalic acids and the alkyd-substituted phthalic and naphthalic acids, and Q and Q represent the 'samequinonyi radicals selected ,from the group consisting of the naphthoquinonyl and anthraquinonyl radicals.

10. An article or manufacture comprising fabric printed with a composition-comprising a vat dye and a dicarboxylic acid diamide represented by the general formula QNI-I-- -A( NHQ in which Ac represents the residue oi. a dicarboxyiic acid selected from the group corisisting of the" saturated and unsaturated aliphatic dicarboxyiic acids of !rom.2-10 carbon atoms, the phthalic acids, the naphthalic acids, the polyhydrophthalic and naphthalic acids and the alkyl-substituted phthalic and naphthalic acids, and Q and 'Q' represent the same quinonyl radicals selected from the group consisting of the naphthoquinonyl and anthraquinonyl radicals.

ROY HERMAN KIENLE. CHESTER ALBERT AMICK.

CERTIFICATE OF CORRECTION.

Patent N ,57 ,102. March 6, 1915.

ROY HERMAN KIENLE, ET AL.

Page 1, first read --dispersion-; and that the said Leslie Frazer (Seal) First Assistant Commissioner of Patents. 

